Herbicidal agents

ABSTRACT

Compounds of the formula AND DERIVATIVES THEREOF, INCLUDING ESTERS, THIOESTERS, AND AMMONIUM AND METAL SALTS THEREOF, WHEREIN R1 is aryl, unsubstituted 2-furyl or 2-furyl substituted at the 5-position by halogen or NO2; R2 and R3 are H or CH3 and X is Cl or Br, are selective defoliating herbicides useful to control weeds in agriculture and horticulture, e.g., cultivation of corn, rice and cotton.

United States Patent 1191 Gante et al.

1451 Feb. 4, 1975 HERBICIDAL AGENTS [75] Inventors: Joachim Gante; Gerhart Schneider,

both of Darmstadt, Germany [73] Assignee: Mei-cit Patent Gesellschaft mit beschrankter Haftung, Darmstadt, Germany [22] Filed: June 25, 1971 [21] Appl. No.: 156,957

[30] Foreign Application Priority Data June 27, 1970 Germany 2031942 [52] US. Cl 71/115, 71/88, 7l/90, 71/93, 71/100, 71/104, 71/107, 71/108,

3,472,646 10/1969 Eue et a1 71/115 FOREIGN PATENTS OR APPLICATIONS 7,102,436 9/1971 Netherlands 71/115 Primary ExaminerJames 0. Thomas, Jr. Attorney, Agent, or Firm-Millen, Raptes & White [57] ABSTRACT Compounds of the formula l R1 c- 0 --COOH and derivatives thereof, including esters, thioesters, and ammonium and metal salts thereof, wherein R is aryl, unsubstituted 2-furyl or 2-furyl substituted at the 5-position by halogen or N0 R and R are H or CH and X is Cl or Br, are selective defoliating herbicides useful to control weeds in agriculture and horticulture, e.g., cultivation of corn, rice and cotton.

8 Claims, No Drawings HERBICIDAL AGENTS BACKGROUND OF THE INVENTION This invention relates to dihalogenated propionic acid derivatives, intermediates in the production thereof and the use thereof as herbicides.

SUMMARY OF THE INVENTION Good herbicidal activity is exhibited by propionic acid derivatives of Formula I wherein X is chlorine or bromine; R, is Ar or unsubstituted 2-furyl or Z-furyl substituted in the -position by halogen or N0 R and R which are identical or different, are hydrogen or methyl; and R, is OH, O-alkyl, O-Ar, O--Ar, OMe, NH NH-alkyl, N-dialkyl, NH--Ar, S-alkyl, S-Ar, S-CN, or SCH CO-O- alkyl.

DETAILED DISCUSSION In the above formula, the alkyl groups can contain l-l 8 carbon atoms and optionally are substituted in the hydrocarbon chain by OH; Ar is phenyl or phenyl monoor di-substituted by halogen, N0 or alkyl or alkoxy of up to 4 carbon atoms; and Me is an alkali metal cation, an optionally substituted ammonium cation, or an equivalent of an alkaline earth metal cation or heavy metal cation. Especially preferred are compounds wherein R is hydroxy, alkoxy, phenoxy, and OMe.

The above-described propionic acid derivatives exhibit leaf-herbicidal activity against a number of difficult-to-com bat grasses in grain, truck crop, and other field and vegetable cultures. At the same time, they are compatible to a surprisingly high degree with the corresponding cultivated plants. Because of an everincreasing grass infestation of cultivated areas, the compounds of Formula I are particularly valuable herbicides which can be employed in cultivated areas to ensure maximum yields in agriculture and horticulture.

The herbicidal agents of this invention contain as an active ingredient an effective concentration of at least one compound of Formula I.

This invention also relates to the novel compounds defined by Formula I. These compounds are furan substituted propionic acid derivatives of Formula la iodo-2-furyl or 5-nitro-2-furyl. Preferred of the compounds wherein R is furyl are those of Formula la wherein Y is H, Cl, Br or N0 Examples of compounds of Formula I wherein R, is aryl are those wherein R is phenyl, 2-, 3-, or 4-chlorophenyl, 2-, 3-, or 4- bromophenyl, 2-, 3-, or 4-nitrophenyl, 2-, 3-, or 4- methylor -ethylphenyl, 2-, 3-, or 4-methoxyor -ethoxyphenyl, 4-isopropylphenyl, 2-chloro-4- methylphenyl, 2-bromo-3-methoxy-5-methylphenyl, 2,4-, 2,6-, or 3,4-dichlorophenyl, 3,5-dinitrophenyl, 3-methyl-4-chlorophenyl, 3-bromo-4-methoxyphenyl, 3,4-dimethylphenyl, 3,4-dimethoxyphenyl, and 2- methoxy-4-chlorophenyl. Preferred compounds of Formula I are those wherein R, is phenyl or phenyl monoor di-substituted in the 3- and/or 4-position by chlorine.

R and R of the herbicidal agents of this invention are hydrogen or methyl. Thus, the effective agents are derivatives of propionic acid, of butyric acid, of isobutyric acid, or of methylethylacetic acid. The compounds derived from propionic acid are preferred, i.e., compounds of Formula I wherein R and R both are hydrogen.

The substituents X in Formula I, which can be identical or different, each is a chlorine or bromine atom. The compounds of Formula I wherein the two substituents X are identical are particularly simple to produce and are thus preferred. These compounds are obtained by reacting the corresponding unsaturated acids or acid derivatives with the selected halogen.

Compounds which exhibit particularly good herbicidal effects are a, B-dichloropropionic acid derivatives of Formulae Ib and Ic:

Ar-CHCl--CHCl-COR,

(Iv) wherein Ar and R, have the values given above.

Depending on R, the active substances of the herbicidal agents of this invention are carboxylic acids, carboxylic acid esters and thioesters, carboxylic acid salts, carboxylic acid thiocyanates, or carboxylic acid amides. Suitable esters are all those of straight-chain and branched alkanols containing up to 18, preferably 1 to 10, carbon atoms and of phenols of the formula Ar-OH wherein Ar is aryl as defined herein. Preferred are the alkyl esters of preferably unbranched alkanols containing up to 10 carbon atoms, phenyl esters, and phenyl esters monoor di-substituted on the phenyl ring by halogen, lower alkyl and/or lower alkoxy (l-4 carbon atoms), particularly those substituted by chlorine, methyl and/or methoxy.

Among the carboxylic acid thioesters of Formula I, of primary importance are those derived from alkyl mercaptans RSSH, thiophenol, and thioglycolic acid esters of the formula HSCH COOR wherein R is alkyl of 1-6 carbon atoms, preferably methyl or ethyl.

Carboxylic acid esters and thioesters of Formula I with a good herbicidal effect which can be produced in an especially economical manner are the a, ,B-dichloro-B-phenylpropionic acid esters of methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, thiophenol, methyl and ethyl mercaptan, as well as of the methyl or ethyl ester of thioglycolic acid.

Examples of carboxylic acid salts of Formula I are ammonium salts, substituted ammonium salts of aliphatic or cycloaliphatic amines containing l-l 8 carbon atoms wherein the hydrocarbon chain or chains thereof are optionally substituted by OH-groups, salts with N- heterocyclics, alkali metal salts, alkaline earth metal salts, and heavy metal salts.

The aliphatic or cycloaliphatic amines can be primary, secondary, or tertiary amines. The hydrocarbon chain or chains can be substituted by up to a total of 4 OH-groups. The individual hydrocarbon chains can be linear or branched and can be mono-, double-, or triple-unsaturated, preferably with CC double bonds.

Of particular importance among the salts of amines are salts of primary amines with longer-chain tertiary alkyl or alkenyl groups, wherein the tertiary carbon atom is preferably vicinal to the nitrogen atom. Mixtures of such amines are commercially available under the name of Primenes (Rohm & Haas Co.).

Examples of amines suitable for forming salts are mono-, di-, and triethylamine', mono-, di-, and tripropylamine and the isomers thereof with branched chains; mono-, di-, and tri-butylamine and the isomers thereof with branched chains, in particular N-tert.- butylamine and isobutylamine; di(2-ethylhexyl)amine; nor tert.-octylamine; N,N'-bis(tert.-octyl)amine; decyland isodecylamine (especially dimethyloctylamine); dodecylamine, particularly tert.-dodecylamine; a 19 a)2-' 2; 11 23 3)2 z' Other amines which are of special importance for the formation of amine salts of Formula I are, for example, mono-, di-, and triethanolamine; mono-, di-, and tri(hydroxypropyl)-amine or mono-, di-, and tri(hydroxybutyUamine, wherein the OH-groups can, in each case, be in the a-, [3-, or 'y-position. Decamine" (Diamond Alkali Co.) and coconut oil amine can also be used. The term coconut oil amine means a mixture of preferably prirr ary amines, the saturated hydrocarbon chains of which contain 6-18 carbon atoms.

As examples of cycloaliphatic amines, cyclohexylamine and cyclopentylamine are preferably employed. Of special importance, of course, are the amines which are economical and readily obtainable on a technical scale. In many cases, it is advantageous to employ mixtures of amines rather than a single amine, since some amines, particularly the longerchain amines, are

available commercially in many instances in the form of mixtures. Also isomeric amines are often not separated but rather are sold as mixtures and can be employed in this form for producing the herbicidal agents of this invention.

Examples of N-heterocyclic amines the salts of which with the acids of Formula I are important as herbicidal agents of this invention are piperidine, pyridine, pyrrolidine and morpholine and alkylated derivatives thereof.

Of the compounds of Formula l wherein R is Me and Me is a metallic cation or an equivalent of such a cation, the sodium, potassium, magnesium, calcium, copper, zinc, manganese and iron salts are particularly suitable.

Finally, of the carboxylic acid amides, i.e., compounds of Formula I wherein R is NH NH-alkyl, N dialkyl or NH--Ar, important amides are those, in particular, which are monosubstituted or Di-substituted by alkyl groups on the nitrogen, i.e., amides of the abovementioned primary and secondary amines. Examples of such amides are N,N-dimethyl amides, anilides, ethyl amides, 2-hydroxyethyl amides, butyl amides, hexyl amides, dodecyl amides and stearyl amides. It is, of course, also possible to utilize mixtures of amides of Formula I, obtainable,'for example, from the corresponding carboxylic acids and from the abovementioned commercial amine mixtures, as the effective substances of the herbicidal agents of this invention.

The herbicidal effect of the effectivecompounds of the agents of the present invention was examined in tests on several of the most troublesome grass types in grain cultures and other field cultures. For this purpose, the effective substances to be tested were dissolved in acetone, mixed with a commercially available emulsifier, and brought to the concentrations set forth herein with water. The test plants on a turntable were sprayed with the solutions of effective agent with a spray gun until dripping wet. After the test plants had remained in the greenhouse for 3 weeks, the condition of the test plants was evaluated.

in Table l are compiled the concentrations (in 76) of the effective compounds of the invention at which at least of the test plants were killed entirely and the remainder were almost killed or damaged to such an extent as to be regarded as being destroyed.

TABLE I Effect of Compounds of Formula I on Undesired Grasses Test Plan! Wild Effective Compound Leaves) Sorghum halepense l-2 Leaves) Meadow Digi- Foxtail l-2 Leaves) Wild Oat

(2-3 Leaves) Silky Bent taria Grass sang. l-2 (2 Leaves) Leaves) Oat 1-2 6 In a comparative test under the above-described con- R R ditions, a compound known to be a grass herbicide was used, i.e., the 4-chlorobutyn-(2)-yl ester of m- C C II chlorocarbanilic acid (m-chlorophenylcarbamic acid). It was found that although this ester caused a strong in- 5 2 4 hibition in the test plants in concentrations from 0.4 to 0.04%, the compound did not kill the plants. whereinR R R and R have the values given for For An equally high effect as the compounds listed in mula l, with chlorine or bromine. Preferably, R is OH. Table l is also exhibited by the following compounds; This reaction is ordinarily conducted in an organic isopropyl ester of a, B-dichloro-B-phenylpropionic to solvent inert with respect to the halogen employed,

acid; e.g., chloroform, carbon tetrachloride, carbon disul-' gmyl ester of a, B dich] r0- B-pheny]propionic acid; t'rde, dimethylformamide, O! glacial acetic acid. The '13- octyl ester f 3- 1i h1 -[3- h 1 i i id; logenation of compounds of Formula ll can also be odium alt of a, Bdich]o o-fl-phenylpropionic acid; conducted in an aqueous medium. It is IlOI always absodiethanolammonium salt of a, ,B-dichloro-B- lutely necessary for the starting material and/or the h l r i i id; final product to be completely dissolved in the solvent cyclohexylammonium salt of a, B-dichloro-fiemployed. The reaction temperatures ordinarily range h l i j id; between C. and the boiling point of the solvent utia, p-di hl -p.(4. h1 h l)- i i id; lized, preferably +l0 C. or above. Occasionally, it is ammonium lt f l3.di hl fl-(4- h1 h l)- 20 advantageous to irradiate the reaction mixture during i i id; the halogenation with visible or ultraviolet light. The diethanolammonium Salt f a, l g 4- reaction time depends essentially on the size of the rechlorophenyl)-propionic acid; acted batch and usually ranges between 15 minutes and ammonium l f fl-di hl -fl-(3 4 di h] 48 hours. The reaction products are isolated in a conh ry i i id; d ventional manner. Insofar as they are insoluble in the Sodium salt f a, /3 di h] -fi-(3 4.di h| h l solvent employed, they are filtered off. Soluble prodpropionic id ucts can be isolated by distilling off the solvent. in additional tests, the influence of the effective com- The effective compounds of the herbicidal agents of pounds of this invention and the comparison comthis invention can also be obtained by substituting one pound on several important cultivated plants was ex- R group by a different R group in compounds of Foramined. For this purpose, these plants were treated mula l. in particular, carboxylic acids of Formula l (R, with the preparations of effective agents in the same H) C be Converted into the Salts 4 manner as described above for the undesired grasses. esters (R O-alkyl -all yl or O--Ar), thioesters (R, The evaluation was conducted 3 weeks after spraying. =S-alkyl, S-Ar or SCh -COO-alkyl) or amides Table II contains in column A the lowest killing conor substituted amides (R,=NH NH-alkyl, NHAr or centration (in percent by weight) (0.4% being the high- N-dialkyl) thereof. est test concentration) and in column B the lowest con- The salts of Formula I are preferably prepared by recentration which still led to an inhibition of the cultiacting the carboxylic acids of Formula I with correvated plants. In this connection, the degree of inhibisponding bases or amines, such as, for example, sodium tion is indicated in a five-value scale (H1 to H5) hydroxide, potassium hydroxide, calcium hydroxide, wherein H1 means a very slight, temporary inhibition ammonia, methylamine, dimethylamine, butylamine, and H5 represents a strong, lasting inhibition. or dibutylamine. Heavy metal salts of Formula I are TABLE ll Effect of Compounds of Formula I on Cultivated Plants Cultivated Plant Wheat Sugar Beet (orn Rice Cotton Effective 1 Compound A B A B A B A B A B a,B-Dichloro-fi-phenylpropionic acid 0.4 0.4/H4 0.4 0.2IH4 0.4 0.4/H3 0.4 0.4/H3 0.4 0.2/H4 Methyl ester of a,,8-di-chloro- [i phenylpropionio acid 04 0.4/H3 0.4 0.4/H2 0.4 no inhibi- 0.4 no inhibi- 0.4 no inhibitron tron tron Control: 4-Chlorobutyn-(2)-yl ester of m-chlorocarbanilic acid 0.4 0.2/H5-H4 0.4 0.1/H4 0.04/H4 0.4-0.1 0.l/H5 0.4 0.l/H5-H4 It can beclearly seen from this table that the effective compounds of the agents of this invention are tolerated more satisfactorily by the cultivated plants than the control, i.e., the reference comound.

Some of the compounds of Formula I are known in the literature. The novel compounds can be prepared v analogously to the conventional compounds. A preferred method is reacting the unsaturated compounds of Formula ll cator. The end point of the reaction can, of course, also measuring device.

The esterification of carboxylic acids of Formula I is preferably effected by reaction with the corresponding alcohol in the presence of a catalytic amount of a suitable acid, for example hydrochloric acid or sulfuric acid. However, the acid can first be converted into a reactive acid derivative, preferably a halogenide, particularly the acid chloride, and this product thereafter reacted with the alcohol corresponding to the desired ester group or preferably with an alcoholate thereof, especially the alkali metal alcoholate. In this way, in particular, the aryl esters (R O-Ar) and the thioesters (R S-alkyl, S-Ar, S-CH COO-alkyl) are produced. In the same manner, the thiocyanates of Formula I are obtained by reacting an acid halogenide with an alkali metal thiocyanate.

The acid amides of Formula 1 (R Nl-l NH-alkyl, NH-Ar, N-dialkyl) are ordinarily obtained by reacting a reactive acid derivative, preferably an acid halogenide, with ammonia of a primary or secondary amine. It is, of course, likewise possible to convert the acid amides (R, NHg) into the N-substituted derivatives by conventional alkylating or arylating methods, respectively. Furthermore, amides can be produced from the ammonium s lts and substitified ammonium salts of Formula I by splitting off water.

The compounds of Formula I can be processed into all forms of application customary for herbicidal agents. Thus, the effective compounds can be utilized in solid or liquid form, in combination with the usual vehicles, fillers, and/or auxiliary agents, as sprayable and/or dusting agents, solutions, or emulsions which can, for example, also be sprayed as aerosols, as well as in the form of dispersions or granulated compositions. Additives which can be employed in this connection are, for example, vehicles or fillers such as bole, kaolin, siliceous chalk (naturally occurring mineral, consisting of kaolinite and quartz), bentonite, ground slate, pyrophyllite, talc, montmorillonite, chalk, dolomite, mica, silicic acid, aluminium or calcium silicate, kieselguhr and ground walnut hulls; wetting agents wherein, depending on the specific use, anionic or cationic or also nonionic surfactants are suitable, including soaps, e.g., sodium laurate; alkyl sulfates or sulfonates, such as sodium dodecyl sulfate or sulfonate; sulfonated and sulfated ethers; sulfonated alkyl fatty acid esters; sulfonated glycol fatty acid esters; quaternary ammonium salts, e.g., trimethylammonium iodide; amines and amides with long aliphatic chains; monoethers of polyglycols with long-chain aliphatic alcohols, e.g., the reaction products of ethylene oxide or polyethylene glycol with higher aliphatic alcohols; monoesters of polyglycols with fatty acids. e.g., oleic acid; monoethers of polyglycols with alkylated phenols; partially esterified polyhydric alcohols, e.g., sorbitan trioleate; partially or completely esterified polyglycol ethers of polyhydric alcohols, e.g., the tristearic acid ester of the polyglycol ether of sorbitan; binders and dispersing agents, e.g., cellulose and the derivatives thereof, e.g., methyl-, ethyl-, hydroxypropyl-, or carboxymethylcellulose, tragacanth, pectins, gum arabic; solvents, e.g., hydrocarbons, including cyclohexane, xylene, solvent naphtha (aromatic hydrocarbon mixtures having boiling points of between 150 and 180), petroleum, especially petroleum fractions having boiling points of between 80 and 200, tetrahydronaphthalene, decahydronaphthalene;

aliphatic alcohols, e.g., methanol, ethanol, isopropanol, isobutanol, n-butanol, or hexanol; glycol ethers, e.g.,

'methyl glycol, ethyl glycol; ketones, e.g., acetone,

methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methylcyclohexanone, dioxane; dimethylformamide, N- methylpyrrolidone; dimethyl sulfoxide; acetonitrile; and mixtures of these solvents. The effective agents can be sold as an emulsion concentrate which, prior to use, is diluted with water in the usual manner. In case agents are employed containing, as the effective substance components, one or more water-soluble compounds, it is, of course, also possible to employ water as the solvent or diluent for the preparation of the concentrate.

The total content of the compound of Formula I in these preparations ranges generally between 1 and 95%, preferably between 20 and 80%. Depending on the desired effect, the climatic conditions, and the type and characteristics of the plants to be treated, the effective agent is applied at a rate of between 0.5 and 50 kg./ha., preferably between 2 and 20 kg./ha. (0.44-44 lbs/acre, preferably 1.8-18 lbs/acre).

Theeffective substances of Formula I are also suitable for use as combination preparations. In particular, theycan b e combined with standard herbicides whose effective spectra can be broadened in a desirable manner by this combination. In particular, the compounds of Formula I can also be combined with growthpromoting herbicides and/or with growth-regulating agents or morphoregulators. Preferably, combinations are prepared which contain, in addition to a compound of Formula I, one or more growth-promoting herbicides from the group of the substituted phenoxyalkanecarboxylic acids or the derivatives thereof and/or one or more hydroxybenzonitriles and/or one or more triazines and/or one or more isothiazoles and/or one or more ureas. In such combined preparations, the proportion of the effective agents of this invention in the total content of effective agents ranges normally between 0.5 and 90%, preferably between 10 and 80%.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

In the following examples, temperatures are in degrees Centigrade. For the formulation of the preparations, the numerical data are percent by weight.

PREPARATION OF THE ACTIVE COMPOUNDS EXAMPLE A A vigorous stream of chlorine is introduced, under agitation and UV irradiation. into a suspension of 500 g. of cinnamic acid in 4 l. of carbon tetrachloride for 5 hours. During this procedure, the cinnamic acid is dissolved, and the temperature rises to about Thereafter, the reaction mixture is allowed to cool, and the thus-crystallized a,B-dichloro-B-phenylpropionic acid is filtered; m.p. l69-l71.

EXAMPLE B A 0.3% solution of ammonia in benzene is added dropwise to a solution of 12 g. of a,,8-dichIoro-B- phenylpropionic acid in 500 ml. of benzene until the reaction mixture reacts neutral. After agitating the mixture for one-half hour, the ammoniuma,B-dichloro-B- phenylpropionate is filtered off; m.p. l75l77.

Analogously, the following compounds are obtained: n-butylammonium-a,,8-dichloro-B-phenylpropionate, m.p. 130 and di-n-butylammonium-a,B-dichloro-[3- phenylpropionate, m.p. 7072.

EXAMPLE C EXAMPLE D A solution of 5 g. of zinc acetate in 40 ml. of water is added, under agitation, to a solution of 12 g. of sodium-a,l3-dichloro-fi-phenylpropionate in 75 ml. of water. The thus-precipitated zinc-afi-dichloro-B- phenylpropionate is filtered and dried; m.p. from 250 (decomposition).

Analogously, copper(ll)-a,B-dichloro-B- phenylpropionate is obtained, m.p. from 210 (decomposition).

EXAMPLE E A solution of g. of afi-dichloro-B- phenylpropionic acid in 100 ml. of absolute ethanol is saturated with gaseous hydrogen chloride and refluxed to the boiling point for two hours. Then, the reaction mixture is concentrated to about one-half of its original volume, and cooled with ice. The thus-crystallized ethyl ester of a,B-dichloro-B-phenylpropionic acid melts at -30.

Analogously, the following compounds are obtained: methyl ester of a,B-dichloro-fi-phenylpropionic acid, m.p. 101 n-propyl ester of a,B-dichloro-/3- phenylpropionic acid n-butyl ester of a,,B-dichloro-B- phenylpropionic acid isobutyl ester of afi-dichloro-B- phenylpropionic acid, b.p. l34-l 39 n-amyl ester of ctfi-dichloro-B-phenylpropionic acid isoamyl ester of a,B-dichloro-B-phenylpropionic acid, bp l50-l55 n-hexyl ester of a,B-dichloro-,B- phenylpropionic acid, b.p.,, l54157 n-octyl ester of a,B-dichloro-B-phenylpropionic acid ethoxycarbonylmethyl thioester of a,B-dichloro-,8- phenylpropionic acid.

EXAMPLE F 20 g. of a,fi-dichloro-B-phenylpropionic acid chloride and 10 g. of sodium phenolate are dissolved in 100 ml. of acetonitrile and agitated for 6 hours at room temperature. Thereafter, the reaction mixture is filtered off from the precipitated sodium chloride and evaporated under reduced pressure. The phenyl ester of afldichloro-fiphenylpropionic acid remains in the form of a yellowish oil which solidifies after allowed to stand for some time and which melts, after recrystallization from petroleum ether, at 5560.

Analogously, the following compounds are obtained:

thiophenyl ester of a,B-dichloro-fl-phenylpropionic acid and 11,,B-dichloro-B-phenylpropionic acid thiocyanate.

EXAMPLE G A solution of 8.6 g. of chlorine in 200 ml. of carbon tetrachloride is added dropwise, under agitation and UV irradiation, to a solution of 13.9 g. of ,8-2- furylacrylic acid in 20 ml. of dimethylformamide at 20 and during the course of 30 minutes. After stirring the reaction mixture for another 15 minutes at 20, it is heated to room temperature and the carbon tetrachloride phase is separated. After the solvent has been distilled off under reduced pressure, there remains 9.5 g. of a,B-dichloro-B-(5-chloro-2-furyl)-propionic acid in the form ofa non-distillable oil.

EXAMPLE H To a suspension of 20 g. of B-Z-furylacrylic acid in 200 ml. of carbon disulfide, 15 ml. of bromine is added dropwise under agitation and at room temperature, during the course of 2 hours. Thereafter, the reaction mixture is heated for 2 hours at 35 and, after cooling,

the thus-crystallized a,B-dibromo-/3-(5-bromo-2- furyl)-propionic acid is filtered off; this compound melts at l34136 with decomposition'after having been recrystallized from benzene.

EXAMPLE I Chlorine is introduced for one hour into a suspension of 6.2 g. of ,8-(5-nitro-2-furyl)-acrylic acid in 50 ml. of glacial acetic acid under UV irradiation at 60. Thereafter, the glacial acetic acid is distilled off under reduced pressure; there remains mB-dichloro-B-(S-nitro- 2-furyl)-propionic acid as a red oil which decomposes while assuming a black color during attempts at distilling this product.

EXAMPLE J A solution of 10.3 g. of 2,4-dichloroaniline in ml.

of chloroform is added dropwise to a solution of 9.5 g.

PREPARATION OF COMPOSITIONS FOR APPLICATION PURPOSES EXAMPLE 1 Spruyable powder:

75.0 "/2 afiDichloro-fi-phenylpropionic acid 0.5 Alkyl naphthalenesulfonute 10.0 '7! Sulfitc waste liquor powder l4.5 /r Kaolin EXAMPLE 2 Sprayable powder:

65 7t Ammonium-afi-dichloro-B-phenylpropionate 8 Oleic acid N-methyltaurine 27 7t Precipitated calcium silicate EXAMPLE 3 Emulsion concentrate:

50 7c afi-Dichloro-B-phenylpropionic acid n-hexyl ester Solvent naphtha Emulsifier (mixture of alkyl aryl sulfonate and nonylphenol polyglycol ether) Emulsion concentrate:

50 7e afiDichloro-B-phenylpropionic acid ethyl ester Cyclohexane Xylene Emulsifier (mixture of alkyl aryl sulfonate and nonylphenol polyglycol ether) EXAMPLE Sprayable powder:

40 aJ3-DichIoro-B-phenylpropionic acid phenyl ester 50 7: Precipitated silicic acid I 7t Alkyl naphthalenesulfonate 9 '/z Sulfite waste liquor powder EXAMPLE 6 Salt formulation:

80 7: Sodium-afi-dichloro-/3-phenylpropionate l5 7! Ammonim sulfate 1 7( Sodium alkyl sulfate 4 Sulfite waste liquor powder 7 2.4-Dichlorophenoxyacetic acid isooctyl ester 35 7: Solvent naphtha l0 7: Dimethylformamide 5 '71 Emulsifier (mixture of alkyl aryl sulfonate and nonylphenol polyglycol ether) EXAMPLE l2 Sprayable powder: 35 afi-Dichloro-fi-t5-chloro-2-furyl)-propi0nic acid methyl ester 10 7c 2-Chloro-4-ethylamino--isopropylamino-l .3,5-

triazine 1 7: Sodium dialkylnaphthalene sulfonate l2 71 Sulfite waste liquor powder 42 7t Bole EXAMPLE l3 Emulsion concentrate: 33 7! a,B-Dichloro-B-( 3-chloro-4-methylphenyl)-propionic acid octyl ester l7 7: 2-Chloro-9-fluorenol-9'carboxylic acid buten-(2)-yl ester l5 '7: Dimethyl sulfoxide 72 Tetrahydronaphthalene 2 74 Methylcellulose 3 '7: 1 Sodium dodecyl sulfonate EXAMPLE l4 Emulsion concentrate:

25 '7: afi-Dichloro-B-phenylpropionic acid n-hexyl I EXAMPLE 7 ester Analogously to Example 1,. 75% strength Sprayable l5 7: 2-Methyl-4-chlorophenoxyacetic acid isooctyl ester 5 7: 9-Fluorenol-9-carboxylic acid n-butyl ester Powders are produced contammg, as the effecpve 5 7t 3.5-Diiodo-4-hydroxybenzonitrile oleylamine salt stance of Formula I, one or more of the followIng com 10 Dimelhylforrnamide ounds. 5 Z: Emulsifier (mixture of polyoxyethylene sorbitan p ester and sodium alkylaryl sulfonate) zmc-a,/3-dichloro-B-phenylpropIonate 3s 71 Xylene n-butylammonium-a,fl-dichloro-B-phenylpropionate EXAMPLE l5 dI-n-butylammon1um-a,/3-drchloro-B- San formumion:

phenylpropionate 30 54 '74 afi-Dichloro-B-phenylpropionic acid Primene" dimethylammfmium'aifi'dichlom'fi 27 71 2 :25-Trichlorophenoxyacetic acid sodium salt phenylproplonate 9 "/1 2-Chloro-9-fluorenol-9-carboxylic acid sodium salt I 8 Sulfite waste liquor powder dichloro B (4 ChIOrOPhEnyI). propmmc dcld 2 71 Sodium dialkyl naphthalenesulfonate afi-drchloro-B-phenylbutyric acid calcium-a,B-dichloro-B-phenylpropionate EXAMPLE lo 30 "/t afi-Dichloro-/3-phenylpropionic acid phenyl ester EXAMPLE 8 18 2-Met h l-4-chlorophenox acetic acid hexyl ester Analogously to Example 3, 50% strength emulsion 6 ggzP' W concentrates are prepared, containing as the active 6 V1 3-Chloro-S-trimethylacetylaminoisothiazolel-carbonitrile agents, one or more of the following comp0unds. 40 5 Alkyl naphthulencsulronm n-propyl ester of afi-dIchloro-B'phenylpropionIc 35 1 Solvent naphtha acid n-amyl ester of a,,B-dichloro-B-phenylpropionic acid octyl ester of a,/3-dichloro-B-phenylpropionic acid ethoxycarbonylmethyl thioester of a,,8-dichloro-B- phenylpropionic acid a,B-dichloro-B-( 3-methoxyphenyl)-propionic Primene salt hexyl ester of a,B-dichloro-B-2-furylpropionic acid EXAMPLE 9 Analogously to Example 4, strength emulsion concentrates are produced, containing as the active agents, one or more of the following compounds:

methyl ester of 0:,B-dichloro-B-phenylpropionic acid ethyl ester of a,B-dichloro-B-(2,4-dichlorophenyl)- propionic acid a,B-dichloro-B-phenylpropionic acid thiocyanate acid,

a,,B-dichloro-B-phenylpropionic acid n-dodecyl amide thiophenyl ester of a,B-dichloro-B- phcnylpropionic acid EXAMPLE l0 Sprzyahle powder:

40 I afi-Dichloro-fi-phen lpropionic acid 20 7t J-Chloro-S-isobutyry amino-4-cyanoisothiuzole I 71 Alkyl naphthalenesult'onatc l2 "/1 Sulfite waste liquor powder 27 7: Bentonite EXAMPLE ll Emulsion concentrate: 25 7c afi-Qijchloro-B-phenylpropionic acid n-dodecyl am e The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

What is claimed is:

1. A method of combatting weed grasses which comprises applying thereto a herbicidally effective amount ofa composition containing as an essential active ingredient at least one of a,B-dichloro-B-phenylpropionic acid or an alkali-metal or ammonium, salt thereof.

2. A method according to claim 1 wherein the essential active ingredient is sodium a,B-dichloro-B-phct1ylpropionate.

3. A method according to claim 1 wherein the essential active ingredient is ammonium a,B-dichloro-B-phenyl-propionate.

4. A method according to claim 1 wherein the essential active ingredient is a,B-dichloro-B-phenylpropionic acid.

5. A method according to claim 1 wherein the composition is applied to a cultivated crop area in an amount effective to substantially inhibit weed grass growth but less than that which is substantially phytotoxic to the cultivated crop.

6. A method according to claim wherein the essential active ingredient is sodium a,l3-dichl0ro-B-phenylpropionate.

acid. 

2. A method according to claim 1 wherein the essential active ingredient is sodium Alpha , Beta -dichloro- Beta -phenyl-propionate.
 3. A method according to claim 1 wherein the essential active ingredient is ammonium Alpha , Beta -dichloro- Beta -phenyl-propionate.
 4. A method according to claim 1 wherein the essential active ingredient is Alpha , Beta -dichloro- Beta -phenyl-propionic acid.
 5. A method according to claim 1 wherein the composition is applied to a cultivated crop area in an amount effective to substantially inhibit weed grass growth but less than that which is substantially phytotoxic to the cultivated crop.
 6. A method according to claim 5 wherein the essential active ingredient is sodium Alpha , Beta -dichloro- Beta -phenyl-propionate.
 7. A method according to claim 5 wherein the essential active ingredient is ammonium Alpha , Beta -dichloro- Beta -phenyl-propionate.
 8. A method according to claim 5 wherein the essential active ingredient is Alpha , Beta -dichloro- Beta -phenylpropionic acid. 